CN102597110B

CN102597110B - Poly carbonate resin composition and products formed

Info

Publication number: CN102597110B
Application number: CN201080050088.8A
Authority: CN
Inventors: 佐佐木一雄
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Chemical Corp; Mitsubishi Rayon Co Ltd
Priority date: 2009-12-10
Filing date: 2010-12-10
Publication date: 2016-05-04
Anticipated expiration: 2030-12-10
Also published as: CN105713366A; EP2511343A1; US20120245265A1; KR101794501B1; CN102597110A; EP2511343A4; WO2011071166A1; KR20120092639A; CN105713366B

Abstract

The present invention relates to poly carbonate resin composition and products formed thereof, the poly carbonate resin composition (X) of this poly carbonate resin composition for comprising polycarbonate resin (A) and aromatic polycarbonate resin (B), this polycarbonate resin (A) comprises construction unit (a), the part that described construction unit (a) carrys out self-structure has the dihydroxy compounds at the position that following general formula (1) represents, wherein, above-mentioned aromatic polycarbonate resin (B) shared ratio in above-mentioned poly carbonate resin composition (X) is more than 30 % by weight, wherein do not comprise that the position that above-mentioned general formula (1) represents is-CH₂The situation of a part of-O-H.

Description

Poly carbonate resin composition and products formed

Technical field

The present invention relates to poly carbonate resin composition and the products formed thereof of a kind of weatherability, the transparency, tone, heat resistance, heat endurance, mouldability and mechanical strength excellence.

Background technology

Polycarbonate resin is generally using bisphenols as monomer component, the superiority such as the performance transparency, heat resistance, mechanical strength are widely used as so-called engineering plastics in the fields such as electric and electronic unit, automotive part, medical part, building materials, film, sheet material, bottle, optical record medium and lens.

But for existing polycarbonate resin, if use under the place that is exposed to for a long time ultraviolet ray and visible ray, tone, the transparency and mechanical strength worsen, therefore near outdoor and lighting device, its use is restricted. And, in the situation that using as various products formeds, there is following problems: when melt molding, antistick characteristic is poor, be difficult to use in transparent material and optical material, etc.

In order to solve such problem, be that ultra-violet absorber, benzoxazine are that the method that ultra-violet absorber adds in polycarbonate resin is extensive known (for example, non-patent literature 1) by benzophenone series ultra-violet absorber, BTA.

Also extensively known in addition, even if polycarbonate resin is also unstable to alkali compositions such as alkali at normal temperatures, also can be hydrolyzed for hindered amine system (HALS) polycarbonate resin, therefore, while the light stabilizer of hindered amine system (HALS) being added in polycarbonate resin, do not there is practicality.

Be used for the bisphenol compound of polycarbonate resin in the past owing to thering is benzene ring structure, therefore ultraviolet radiation absorption is large, this can cause the light resistance of polycarbonate resin to worsen, aliphatic dihydroxy compounds or the ester ring type dihydroxy compounds that does not have benzene ring structure in molecular skeleton if therefore use, the ring-type dihydroxy compounds monomeric unit in molecule as isobide with ehter bond, can expect in principle that light resistance is improved.

Wherein, the heat resistance of the polycarbonate resin using the isobide being obtained by biological substance resource as monomer and mechanical strength excellence, therefore carried out a large amount of research (for example, patent documentation 1～7) to it in recent years.

Also extensively known in addition, add as (patent documentations 8) such as BTA system, benzophenone series and the cyanoacrylate systems of ultra-violet absorber having used in the poly carbonate resin composition in molecular skeleton without material benzene ring structure, there is ehter bond in molecule as isobide, isomannite and different iditol etc..

Prior art document

Patent documentation

Patent documentation 1: No. 2004/111106th, International Publication

Patent documentation 2: TOHKEMY 2006-232897 communique

Patent documentation 3: TOHKEMY 2006-28441 communique

Patent documentation 4: TOHKEMY 2008-24919 communique

Patent documentation 5: TOHKEMY 2009-91404 communique

Patent documentation 6: TOHKEMY 2009-91417 communique

Patent documentation 7: TOHKEMY 2008-274007 communique

Patent documentation 8: TOHKEMY 2007-70391 communique

Non-patent literature

Non-patent literature 1: polycarbonate resin handbook, on August 28th, 1992, Nikkan Kogyo Shimbun's distribution, this single-minded volume

Summary of the invention

The problem that invention will solve

But, add ultra-violet absorber as recorded in non-patent literature 1 time, although confirm the improvement of ultraviolet postradiation tone etc., have following problem: cause the deterioration of tone, heat resistance and the transparency of resin originally, or volatilization and pollute metal die in the time of moulding; Etc..

In addition, for aliphatic dihydroxy compounds and ester ring type dihydroxy compounds as recorded in above-mentioned patent documentation 1～7, as isobide, in molecule, there is the ring-type dihydroxy compounds of ehter bond, it does not have phenolic hydroxyl group, therefore be difficult to carry out polymerization by the extensive known interface method of method for making of the polycarbonate resin as taking bisphenol-A as raw material, conventionally, utilize the method that is called as ester-interchange method or fusion method to manufacture.

In the method, make the carbonic diesters such as above-mentioned dihydroxy compounds and diphenyl carbonate carry out ester exchange with more than 200 DEG C high temperature under the existence of base catalyst, the phenol generating as accessory substance etc. is removed to outside system, thereby carries out polymerization, obtain polycarbonate resin.

But, compared with the polycarbonate resin obtaining with the monomer that uses bisphenol-A etc. to there is phenolic hydroxyl group, use the poor heat stability of the polycarbonate resin that the monomer without phenolic hydroxyl group as described above obtains, therefore in the polymerization at high temperature carried out and in moulding, meeting generation is painted, and result there will be the problem that causes light resistance to worsen by absorbing ultraviolet ray and visible ray.

Wherein, have the monomer of ehter bond in the case of using as isobide in molecule, tone worsens significantly, requires significantly improvement. In addition, as various products formed in the situation that, at high temperature carry out melt molding, now also require the material of good thermal stability, mouldability, antistick characteristic excellence.

In addition, add ultra-violet absorber as recorded in patent documentation 8 time, there is the problem that causes the color harmony heat resistance of resin originally and the transparency deterioration based on weather resistance test.

The object of the invention is to eliminate above-mentioned existing problem, poly carbonate resin composition and the products formed thereof of a kind of weatherability, the transparency, tone, heat resistance, heat endurance, mouldability and mechanical strength excellence is provided.

For the scheme of dealing with problems

In order to solve above-mentioned problem, the inventor has carried out repeatedly deep research, found that following poly carbonate resin composition not only has excellent light resistance, and there is the excellent transparency, tone, heat resistance, heat endurance, mouldability and mechanical strength, completed thus the present invention; The poly carbonate resin composition (X) of this poly carbonate resin composition for comprising polycarbonate resin (A) and aromatic polycarbonate resin (B), this polycarbonate resin (A) comprises construction unit (a), the part that described construction unit (a) carrys out self-structure has the dihydroxy compounds at the position that following general formula (1) represents, above-mentioned aromatic polycarbonate resin (B) shared ratio in above-mentioned poly carbonate resin composition (X) is more than 30 % by weight.

(wherein do not comprise that the position that above-mentioned general formula (1) represents is-CH₂Situation when-O-H a part of)

, main points of the present invention are following [1]～[8].

[1] a kind of poly carbonate resin composition, its poly carbonate resin composition (X) for comprising polycarbonate resin (A) and aromatic polycarbonate resin (B), this polycarbonate resin (A) comprises construction unit (a), the part that described construction unit (a) carrys out self-structure has the dihydroxy compounds at the position that following general formula (1) represents, it is characterized in that, above-mentioned aromatic polycarbonate resin (B) shared ratio in above-mentioned poly carbonate resin composition (X) is more than 30 % by weight.

(wherein do not comprise that the position that above-mentioned general formula (1) represents is-CH₂The situation of a part of-O-H)

[2] poly carbonate resin composition as described in [1], it is characterized in that, be at blackboard temperature that 63 DEG C, relative humidity are 50%, the rainfall spray time of every 1 hour is under the environment of 12 minutes, use sun shine carbon arc lamp with discharge voltage 50V, discharge current 60A, the formed body (thickness 3mm) being obtained by above-mentioned poly carbonate resin composition moulding to be carried out after 500 hours treatment with irradiation, total light transmittance is more than 85%, and the difference of yellow colour index (YI) value of these treatment with irradiation front and back is below 10.

[3] poly carbonate resin composition as described in [1] or [2], is characterized in that, the dihydroxy compounds that a part for said structure has the position of following general formula (1) expression is the dihydroxy compounds that following general formula (2) represents.

[4] if [1] is to the poly carbonate resin composition as described in any one of [3], it is characterized in that, with respect to mixture 100 weight portions of above-mentioned polycarbonate resin (A) and above-mentioned aromatic polycarbonate resin (B), the ultra-violet absorber more than also comprising 0.0001 weight portion and below 1 weight portion.

[5] if [1] is to the poly carbonate resin composition as described in any one of [4], it is characterized in that, with respect to mixture 100 weight portions of above-mentioned polycarbonate resin (A) and above-mentioned aromatic polycarbonate resin (B), also comprising 0.001 weight portion hindered amine above and below 1 weight portion is light stabilizer.

[6] if [1] is to the poly carbonate resin composition as described in any one of [5], it is characterized in that, with respect to mixture 100 weight portions of above-mentioned polycarbonate resin (A) and above-mentioned aromatic polycarbonate resin (B), the antioxidant more than also comprising 0.0001 weight portion and below 1 weight portion.

[7] if [1] is to the poly carbonate resin composition as described in any one of [6], it is characterized in that, with respect to mixture 100 weight portions of above-mentioned polycarbonate resin (A) and above-mentioned aromatic polycarbonate resin (B), the releasing agent more than also comprising 0.0001 weight portion and below 2 weight portions.

[8] polycarbonate resin moldings, is characterized in that, this polycarbonate resin moldings is by [1] to the poly carbonate resin composition moulding described in any one of [7] is obtained.

Invention effect

According to the present invention, can provide poly carbonate resin composition and the products formed thereof of a kind of weatherability, the transparency, tone, heat resistance, heat endurance, mouldability and mechanical strength excellence.

Detailed description of the invention

Below, embodiments of the present invention are elaborated, but the explanation of the technical characterictic of the following stated is only an example (typical example) of embodiments of the present invention, only otherwise exceed its main points, the invention is not restricted to following content.

Obtain by ester exchange reaction polycondensation taking dihydroxy compounds and carbonic diester as raw material for polycarbonate resin of the present invention (A), the part that above-mentioned dihydroxy compounds contains structure has the dihydroxy compounds (following, sometimes referred to as " dihydroxy compounds ") at the position of following general formula (1) expression.

, at least comprise from the construction unit of dihydroxy compounds with the position that following general formula (1) represents for polycarbonate resin of the present invention (A).

As for dihydroxy compounds of the present invention, as long as having the position of above-mentioned general formula (1) expression, a part for structure is not particularly limited, specifically, and for example, the oxyalkylene glycols such as diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, 9, two (4-(2-hydroxyl-oxethyl) phenyl) fluorenes of 9-, 9, two (4-(2-the hydroxyl-oxethyl)-3-aminomethyl phenyl) fluorenes of 9-, 9, two (4-(2-the hydroxyl-oxethyl)-3-isopropyl phenyl) fluorenes of 9-, 9, two (4-(2-the hydroxyl-oxethyl)-3-isobutyl phenenyl) fluorenes of 9-, 9, two (4-(2-the hydroxyl-oxethyl)-3-tert-butyl-phenyl) fluorenes of 9-, 9, two (4-(2-the hydroxyl-oxethyl)-3-cyclohexyl phenyl) fluorenes of 9-, 9, two (4-(2-the hydroxyl-oxethyl)-3-phenyl) fluorenes of 9-, 9, two (the 4-(2-hydroxyl-oxethyl)-3 of 9-, 5-3,5-dimethylphenyl) fluorenes and 9, two (4-(2-the hydroxyl-oxethyl)-3-tert-butyl group-6-aminomethyl phenyl) fluorenes of 9-, 9, two (4-(3-hydroxyl-2 of 9-, 2-dimethyl propoxyl group) phenyl) fluorenes etc. has aromatic group and has and the compound of the ether of aromatic group bonding at main chain at side chain, the spiroglycol that the dihydroxy compounds representing taking following general formula (2) represents as the anhydrous sugar alcohol of representative and following formula (3) or following formula (4) etc. has the compound of cyclic ether structure.

Wherein, the aspect of the tone of reactive during from the easiness that obtains, processing, polymerization and the polycarbonate resin (A) that obtains, the preferably oxyalkylene glycols such as diethylene glycol (DEG), triethylene glycol and there is the compound of cyclic ether structure, having in the compound of cyclic ether structure, preferably there are 2 above ring structures.

In addition, from stable on heating aspect, the compound with cyclic ether structure that the dihydroxy compounds preferably representing taking following formula (2) represents as anhydrous sugar alcohol and the following formula (3) of representative, the dihydroxy compounds particularly preferably representing taking following formula (2) is the anhydrous sugar alcohol of representative.

According to the performance that requires of obtained polycarbonate resin (A), these dihydroxy compounds can use separately, also can be used in combination of two or more.

As the dihydroxy compounds of above-mentioned general formula (2) expression, can enumerate isobide, isomannite and the different iditol of the relation of steric isomer. These compounds can use separately one, also can be used in combination of two or more.

Among these dihydroxy compounds, from the sunproof aspect of polycarbonate resin (A), preferably use does not have the dihydroxy compounds of aromatic ring structure. Wherein, isobide can obtain through dehydrating condensation by the D-sorbite of the various starch manufactures that exist in a large number and easily obtain of the resource by derive from plant, from the aspect of the easiness, light resistance, optical characteristics, mouldability, heat resistance and the neutral carbon that obtain and manufacture, isobide is most preferred.

Can comprise from above-mentioned and (hereinafter be sometimes referred to as " other dihydroxy compounds " for the dihydroxy compounds beyond dihydroxy compounds of the present invention for polycarbonate resin of the present invention (A). ) construction unit, the part that optimization polycarbonate resin comprises to come self-structure in the entire infrastructure unit from dihydroxy compounds has the construction unit (a) of the dihydroxy compounds at the position that above-mentioned general formula (1) represents.

With respect to the entire infrastructure unit from dihydroxy compounds, the structure that a part of carrying out self-structure has a dihydroxy compounds at the position that above-mentioned general formula (1) represents be preferably 20 % by mole above, more preferably 30 % by mole above, more preferably more than 40 % by mole. In addition, be preferably 90 % by mole following, more preferably 80 % by mole following, more preferably below 75 % by mole.

Wherein, in the situation that thering is aromatic rings, preferably use the polycarbonate resin with polycarbonate resin (B) different structure.

By using these other dihydroxy compounds, can obtain the flexibility of polycarbonate resin (A) improvement, mouldability improve texts, if but from the construction unit of other dihydroxy compounds containing proportional too much, can cause reduction and the stable on heating reduction of mechanical properties.

As other dihydroxy compounds, for example, can enumerate ethylene glycol, 1,3-PD, 1,2-PD, BDO, 1,3-BDO, 1,2-butanediol, 1, the aliphatic dihydroxy compounds such as 5-heptandiol and 1,6-hexylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tristane dimethanol, pentacyclopentadecandimethanol dimethanol, 2,6-naphthalane dimethanol, 1,5-naphthalane dimethanol, 2,3-naphthalane dimethanol, 2,3-norcamphane dimethanol, 2, the dihydroxy compounds of the ester ring type hydrocarbon such as 5-norcamphane dimethanol and 1,3-adamantane dimethanol, two (4-hydroxyphenyl) propane [=bisphenol-A] of 2,2-, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane of 2,2-, two (4-hydroxyl-3, the 5-diethyl phenyl) propane of 2,2-, two (4-hydroxyl-(3, the 5-diphenyl) phenyl) propane of 2,2-, two (4-hydroxyl-3, the 5-dibromo phenyl) propane of 2,2-, two (4-hydroxyphenyl) pentanes of 2,2-, 2,4 '-dihydroxy-diphenyl methane, two (4-hydroxyphenyl) methane, two (4-hydroxyl-5-nitrobenzophenone) methane, two (4-hydroxyphenyl) ethane of 1,1-, two (4-hydroxyphenyl) pentanes of 3,3-, two (4-hydroxyphenyl) cyclohexanes of 1,1-, two (4-hydroxyphenyl) sulfone, 2,4 '-dihydroxy-diphenyl sulfone, two (4-hydroxyphenyl) thioether, 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxy-3,3 '-dichloro diphenyl ether, two (4-(2-hydroxyl-oxethyl-2-methyl) phenyl) fluorenes of 9,9-, the aromatic series bisphenols such as two (4-hydroxyphenyl) fluorenes of 9,9-and two (the 4-hydroxy-2-methyl phenyl) fluorenes of 9,9-.

Wherein, from the sunproof aspect of polycarbonate resin (A), in preferred molecular structure, do not there is the dihydroxy compounds of aromatic ring structure, i.e. the dihydroxy compounds of aliphatic dihydroxy compounds and/or ester ring type hydrocarbon.

As aliphatic dihydroxy compounds, particularly preferably 1,3-PD, BDO and 1,6-hexylene glycol.

The dihydroxy compounds of ester ring type hydrocarbon is to have the hydrocarbon skeleton of circulus and the compound of 2 hydroxyls. Hydroxyl can with circulus Direct Bonding, also can be by substituting group and circulus bonding. In addition, circulus can be monocycle, can be also many rings. As the dihydroxy compounds of ester ring type hydrocarbon, particularly preferably 1,4-CHDM and tristane dimethanol.

Can contain the stabilizing agents such as reducing agent, antioxidant, deoxidier, light stabilizer, antiacid, pH stabilizing agent and heat stabilizer for dihydroxy compounds of the present invention, particularly, due to apt to deteriorate for dihydroxy compounds of the present invention under acid condition, therefore preferably contain alkaline stabiliser.

As alkaline stabiliser, can enumerate hydroxide, carbonate, phosphate, phosphite, hypophosphites, borate, the soap of the metal of 1 family in long period type periodic table (NomenclatureofInorganicChemistryIUPACRecommendations2005) or 2 families, TMAH, tetraethyl ammonium hydroxide, TPAOH, TBAH, trimethyl ethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, trimethylphenyl ammonium hydroxide, triethyl group ammonium hydroxide, triethyl group benzylic hydrogens amine-oxides, triethyl group phenyl ammonium hydroxide, tributyl benzylic hydrogens amine-oxides, tributyl phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyl triphenyl ammonium hydroxide, the alkaline ammonium compounds such as methyl triphenyl ammonium hydroxide and butyl triphenyl ammonium hydroxide, and 4-aminopyridine, PA, N, the amine compounds such as N-dimethyl-4-aminopyridine, 4-diethyl amino yl pyridines, 2 hydroxy pyrimidine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylamino imidazoles, 2-methoxyl group imidazoles, imidazoles, 2-mercaptoimidazole, glyoxal ethyline and aminoquinoline.

Wherein, the aspect of the easiness of removing from its effect and distillation described later, is preferably phosphate and the phosphite of sodium or potassium, wherein more preferably sodium hydrogen phosphate and hydrogen phosphite disodium.

Content for these alkaline stabilisers of dihydroxy compounds of the present invention is not particularly limited, and conventionally, with respect to for dihydroxy compounds of the present invention, is preferably 0.0001 % by weight～1 % by weight, 0.001 % by weight～0.1 % by weight more preferably. By being more than this lower limit, can fully obtain the rotten effect preventing for dihydroxy compounds of the present invention. In addition, by being below this upper limit, can prevent the modification for dihydroxy compounds of the present invention.

In addition, if will contain using as the manufacture raw material of polycarbonate resin for dihydroxy compounds of the present invention of these alkaline stabilisers, alkaline stabiliser itself becomes polymerization catalyst, not only be difficult to control polymerization speed and quality, and can cause the deterioration of initial stage tone, its result worsens the light resistance of products formed, and therefore as before the manufacture raw material of polycarbonate resin, preferably alkaline stabiliser is removed in spent ion exchange resin and distillation etc.

When for dihydroxy compounds of the present invention, to be isobide etc. have the material of cyclic ether structure, its because of oxygen easily oxidized at leisure, the decomposition therefore causing for anti-block in the time preserving and manufacture, preferably do not sneak into moisture, and, use deoxidier etc., or process under nitrogen atmosphere.

If isobide is oxidized, produce sometimes the analytes such as formic acid. For example, if the manufacture raw material by the isobide that contains these analytes as polycarbonate resin, likely not only cause the painted of obtained polycarbonate resin, or make physical property significantly deteriorated, and can impact polymerisation, likely cannot obtain the polymer of HMW, therefore not preferred.

For obtain not containing above-mentioned oxidation Decomposition thing for dihydroxy compounds of the present invention, and, in order to remove above-mentioned alkaline stabiliser, preferably distill and refines. Distillation now can be simple distillation, also can, for continuous still, be not particularly limited.

As the condition of distillation, preferably under the inert gas atmosphere such as argon or nitrogen, under reduced pressure implement distillation, in order to suppress the modification that causes of heat, preferably under the condition 250 DEG C below, carry out, more preferably below 200 DEG C, more preferably below 180 DEG C.

Preferably utilize such distillation refining, make formic acid content in dihydroxy compounds used in the present invention be 20 ppm by weight following, more preferably 10 ppm by weight following, be particularly preferably below 5 ppm by weight.

By making above-mentioned formic acid content in above-mentioned scope, when containing the above-mentioned dihydroxy compounds for dihydroxy compounds of the present invention as the manufacture raw material of polycarbonate resin, can under the condition of not damaging polymerisation reactivity, manufacture the polycarbonate resin (A) of tone and excellent heat stability. The mensuration of formic acid content utilizes the chromatography of ions to carry out.

Can, to comprise the above-mentioned dihydroxy compounds for dihydroxy compounds of the present invention and carbonic diester as raw material, obtain by ester exchange reaction polycondensation for polycarbonate resin of the present invention (A).

As used carbonic diester, conventionally can enumerate the material that following general formula (5) represents. These carbonic diesters can use separately one, also can be use mixing two or more.

(in general formula (5), A¹And A²Independently of one another for replace or without the carbon number replacing be 1～carbon number be 18 aliphatic group or replace or without the aromatic group replacing)

The carbonic diester representing as above-mentioned general formula (5), for example, can enumerate diphenyl carbonate, carboxylol ester etc. and replace diphenyl carbonate, dimethyl carbonate, diethyl carbonate and dimethyl dicarbonate butyl ester etc. Wherein, be preferably diphenyl carbonate and replace diphenyl carbonate, being particularly preferably diphenyl carbonate.

It should be noted that, when carbonic diester contains the impurity such as chloride ion, suppress sometimes polymerisation, or the tone of obtained polycarbonate resin is worsened, therefore preferably use and wait and carried out refining carbonic diester by distillation as required.

Make as mentioned above to comprise for polycarbonate resin of the present invention (A) carbonic diester representing for dihydroxy compounds and the above-mentioned general formula (5) of dihydroxy compounds of the present invention and carry out ester exchange reaction, thereby manufacture polycarbonate resin.

In more detail, make it carry out ester exchange, and using the monohydroxy compound generating as accessory substance etc. except going to system, thereby obtain for polycarbonate resin of the present invention (A). In this case, conventionally under existing, catalyst for ester exchange reaction carries out polycondensation by ester exchange reaction.

The catalyst for ester exchange reaction that can use during for the manufacture of polycarbonate resin of the present invention (A) (following, sometimes referred to as catalyst, polymerization catalyst. ) can exert an influence to the light transmittance at wavelength 350nm place and yellow colour index value especially.

As used catalyst, among light resistance, the transparency, tone, heat resistance, heat endurance and the mechanical strength of the polycarbonate resin (A) of manufacturing, do not limit as long as particularly can meet light resistance.

As above-mentioned catalyst, for example, can enumerate the alkali compounds such as 1 family or metallic compound, alkaline boron compound, alkaline phosphating compound, alkaline ammonium compound and the amine compound of 2 families (following, also referred to as " 1 family ", " 2 family ") in long period type periodic table. Preferably use 1 family's metallic compound and/or 2 family's metallic compounds.

Can also share the alkali compounds such as alkaline boron compound, alkaline phosphating compound, alkaline ammonium compound and amine compound together with 1 family's metallic compound and/or 2 family's metallic compounds complementaryly, but particularly preferably only use 1 family's metallic compound and/or 2 family's metallic compounds.

In addition, as the form of 1 family's metallic compound and/or 2 family's metallic compounds, conventionally preferably use with the form of the salt such as hydroxide or carbonate, carboxylate, phenolate. From the aspect of the easiness of the easiness that obtains and processing, preferably hydroxide, carbonate and acetate, from the aspect of color harmony polymerization activity, preferably acetate.

As 1 family's metallic compound, for example, can enumerate NaOH, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium acid carbonate, saleratus, lithium bicarbonate, caesium bicarbonate, sodium carbonate, potash, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, odium stearate, potassium stearate, lithium stearate, stearic acid caesium, sodium borohydride, potassium borohydride, lithium borohydride, hydroboration caesium, phenylboric acid sodium, phenylboric acid potassium, phenylboric acid lithium, phenylboric acid caesium, Sodium Benzoate, Potassium Benzoate, lithium benzoate, benzoic acid caesium, sodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphoric acid hydrogen two lithiums, phosphoric acid hydrogen two caesiums, disodium phenylphosphate, phosphenylic acid dipotassium, phosphenylic acid two lithiums, phosphenylic acid two caesiums, sodium alkoxide, potassium alkoxide, lithium alkoxide, caesium alkoxide, sodium phenates, potassium phenates, lithium phenates, caesium phenates, the disodium salt of bisphenol-A, the di-potassium of bisphenol-A, the dilithium salt of bisphenol-A, two cesium salts of bisphenol-A etc. wherein preferred lithium compound.

As 2 family's metallic compounds, for example, can enumerate calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, brium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, dolomol and strontium stearate etc.

Wherein preferably magnesium compound, calcium compound and barium compound, the aspect from polymerization activity with the tone of the polycarbonate resin obtaining, further preferably magnesium compound and/or calcium compound, most preferably calcium compound.

As alkaline boron compound, for example, can enumerate sodium salt, sylvite, lithium salts, calcium salt, barium salt, magnesium salts and the strontium salt etc. of tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethyl ethyl boron, trimethyl benzyl boron, trimethylphenyl boron, triethyl group methyl boron, triethyl group benzyl boron, triethyl group phenyl boron, tributyl benzyl boron, tributyl phenyl boron, tetraphenyl boron, benzyl triphenyl borine, methyl triphenyl boron and butyl triphenyl boron etc.

As alkaline phosphating compound, for example, can enumerate triethyl phosphine, three n-pro-pyl phosphines, tri isopropyl phosphine, tri-n-butyl phosphine, triphenylphosphine, tributylphosphine with quaternary alkylphosphonium salt etc.

As alkaline ammonium compound, for example, can enumerate TMAH, tetraethyl ammonium hydroxide, TPAOH, TBAH, trimethyl ethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, trimethylphenyl ammonium hydroxide, triethyl group ammonium hydroxide, triethyl group benzylic hydrogens amine-oxides, triethyl group phenyl ammonium hydroxide, tributyl benzylic hydrogens amine-oxides, tributyl phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyl triphenyl ammonium hydroxide, methyl triphenyl ammonium hydroxide and butyl triphenyl ammonium hydroxide etc.

As amine compound, for example, can enumerate 4-aminopyridine, PA, N, N-dimethyl-4-aminopyridine, 4-diethyl amino yl pyridines, 2 hydroxy pyrimidine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylamino imidazoles, 2-methoxyl group imidazoles, imidazoles, 2-mercaptoimidazole, glyoxal ethyline and aminoquinoline etc.

With respect to the every 1mol in the whole dihydroxy compounds that use in polymerization, the consumption of above-mentioned polymerization catalyst is preferably 0.1 μ mol～300 μ mol, 0.5 μ mol～100 μ mol more preferably. Wherein, when compound that use contains at least one metal in the group of selecting 2 group compositions in free lithium and long period type periodic table, while particularly using magnesium compound and/or calcium compound, in amount of metal, with respect to the every 1mol in above-mentioned whole dihydroxy compounds, be preferably 0.1 μ mol above, more preferably 0.5 μ mol above, be particularly preferably 0.7 μ mol more than. In addition as the upper limit, be preferably 20 μ mol following, more preferably 10 μ mol following, more preferably 3 μ mol following, be particularly preferably 1.5 μ mol following, most preferably be below 1.0 μ mol.

Be more than above-mentioned lower limit by making the amount of polymerization catalyst, have the following advantages: prevent that polymerization speed is slack-off; In order to obtain the polycarbonate resin (A) of desired molecular weight, need not set polymerization temperature compared with highland.

In addition, can improve the color harmony light resistance of obtained polycarbonate resin (A), prevent the volatilization in polymerization way of unreacted raw material, keep, containing being useful on the dihydroxy compounds of dihydroxy compounds of the present invention and the molar ratio of the carbonic diester that above-mentioned general formula (5) represents, reaching desired molecular weight.

In addition, be below the above-mentioned upper limit by making the consumption of polymerization catalyst, can prevent the deterioration of the tone of obtained polycarbonate resin (A), improve the light resistance of polycarbonate resin (A).

In addition, while using the replacement diphenyl carbonates such as diphenyl carbonate and carboxylol ester to manufacture for polycarbonate resin of the present invention (A) as the carbonic diester of above-mentioned general formula (5) expression, the raw phenol of by-product and fortified phenol, it inevitably remains in polycarbonate resin (A), because phenol and fortified phenol also have aromatic rings, thereby not only absorb sometimes ultraviolet ray, cause light resistance to worsen, and there is peculiar smell sometimes also moulding can be caused time.

In polycarbonate resin (A), after common batch reactions, contain the aromatic monohydroxy compound that the raw phenol of more than 1000 ppm by weight by-product etc. has aromatic rings, from the aspect of light resistance and reduction peculiar smell, preferably use the horizontal reactor of devolatilization excellent performance or the extruder with vaccum exhaust outlet, preferably make the content of this aromatic monohydroxy compound be preferably 700 ppm by weight following, more preferably 500 ppm by weight following, be particularly preferably below 300 ppm by weight. Wherein, because industrial being difficult to removes completely, the lower limit of the content of aromatic monohydroxy compound is generally 1 ppm by weight.

It should be noted that, according to the difference of used raw material, these aromatic monohydroxy compounds can have substituting group certainly, and for example, can have carbon number is alkyl below 5 etc.

In addition, if contain in a large number 1 family's metal in polycarbonate resin (A), wherein for sodium, potassium and caesium, particularly lithium, sodium, potassium, caesium, likely tone is caused to harmful effect, this metal is not only sneaked into by used catalyst, also may sneak into from raw material or reaction unit. Therefore their total amounts in polycarbonate resin (A) in amount of metal be conventionally preferably below 1 ppm by weight, more preferably below 0.8 ppm by weight, more preferably below 0.7 ppm by weight.

Amount of metal in polycarbonate resin (A) can be measured by following manner: utilize the methods such as wet type ashing to reclaim after the metal in polycarbonate resin, use the methods such as atom is luminous, atom extinction, inductively coupled plasma (ICP) to measure amount of metal.

To make containing being useful on the dihydroxy compounds of dihydroxy compounds of the present invention and the carbonic diester of above-mentioned general formula (5) obtains by ester exchange reaction polycondensation for polycarbonate resin of the present invention (A), as dihydroxy compounds and the preferably evenly mixing before ester exchange reaction of carbonic diester of raw material.

The temperature of mixing be generally 80 DEG C above, be preferably more than 90 DEG C, its upper limit be generally 250 DEG C following, be preferably 200 DEG C following, more preferably below 150 DEG C. More than being wherein suitably 100 DEG C and below 120 DEG C.

If the temperature of mixing is more than above-mentioned lower limit, dissolution velocity accelerates, solubility is abundant, the unfavorable condition such as therefore can prevent from solidifying. If the temperature of mixing, below the above-mentioned upper limit, can prevent that the heat of dihydroxy compounds is deteriorated, its result, the tone of the polycarbonate resin obtaining improves, and can fully obtain light resistance.

About by the raw material as for polycarbonate resin of the present invention (A), containing the operation that is useful on carbonic diester that the dihydroxy compounds of dihydroxy compounds of the present invention and above-mentioned general formula (5) represent and mixes, preferably oxygen concentration is that 10vol% is following, 0.0001vol%～10vol% more preferably. Wherein, from the aspect that prevents that tone from worsening, preferably at 0.0001vol%～5vol%, carry out under particularly preferably in the atmosphere of 0.0001vol%～1vol%.

In order to obtain for polycarbonate resin of the present invention (A), with respect to the dihydroxy compounds that is useful on dihydroxy compounds of the present invention that contains using in reaction, the carbonic diester that above-mentioned general formula (5) represents preferably uses with 0.90～1.20 molar ratio, more preferably 0.95～1.10 molar ratio.

Be more than above-mentioned lower limit by making above-mentioned molar ratio, the terminal hydroxyl that can suppress the polycarbonate resin of manufacturing increases, and improves the heat endurance of polymer, and painted while preventing moulding promotes the speed of ester exchange reaction to obtain desired HMW body.

In addition, be below the above-mentioned upper limit by making above-mentioned molar ratio, can accelerate the speed of ester exchange reaction, easily manufacture the polycarbonate resin (A) of desired molecular weight. By accelerating ester exchange reaction speed, the thermal process can suppress polymerisation time, its result, can improve the color harmony light resistance of obtained polycarbonate resin.

In addition, with respect to the dihydroxy compounds containing being useful on dihydroxy compounds of the present invention, the molar ratio of the carbonic diester that above-mentioned general formula (5) represents does not increase, can suppress the remaining carbonic diester amount in obtained polycarbonate resin (A), prevent that their from absorbing ultraviolet ray and the light resistance of polycarbonate resin is worsened.

For the concentration of the remaining carbonic diester of polycarbonate resin of the present invention (A) be preferably 200 ppm by weight following, more preferably 100 ppm by weight following, more preferably 60 ppm by weight following, be particularly preferably below 30 ppm by weight. In fact polycarbonate resin (A) comprises unreacted carbonic diester sometimes, and the lower limit of concentration is generally 1 ppm by weight.

In the present invention, for the method that makes dihydroxy compounds and carbonic diester polycondensation, it is under above-mentioned catalyst exists, conventionally implements with the multistage with more than 2 reactors. The form of reaction can be any method in the combination of batch-type, continous way or batch-type and continous way.

Preferably, at the polymerization initial stage, obtain prepolymer with relative low temperature, low vacuum, in the polymerization later stage, make molecular weight rise to predetermined value with relatively-high temperature and high vacuum, from the sunproof aspect of color harmony, importantly select aptly the pressure in jacket temperature and Nei Wen and the reaction system in each molecular weight stage.

For example, if one of appointing in transformation temperature and pressure too quickly before polymerisation reaches predetermined value, unreacted monomer distillates, the mol ratio of dihydroxy compounds and carbonic diester is upset, cause the reduction of polymerization speed, or cannot obtain having predetermined molecular weight and the polymer of end group, its result, likely cannot realize the object of the present application.

In addition, for the amount of the monomer that suppresses to distillate, in polymer reactor, using reflux cooler is effectively, and particularly in the unreacted monomer composition reactor at many polymerization initial stages, its effect is large.

The temperature that is directed into the cold-producing medium of reflux cooler can the suitable selection according to used monomer, conventionally the temperature that, is directed into the cold-producing medium of reflux cooler is preferably 45 DEG C～180 DEG C, more preferably 80 DEG C～150 DEG C at the entrance of this reflux cooler, is particularly preferably 100 DEG C～130 DEG C.

Be below the above-mentioned upper limit by making the temperature of the cold-producing medium that is directed into reflux cooler, can improve capacity of returns, fully obtain its effect. In addition, by being more than above-mentioned lower limit, can improving the original distillation that will distill the monohydroxy compound of removing and remove efficiency.

As cold-producing medium, for example, use warm water, steam and thermal medium wet goods, preferably steam and thermal medium oil.

In order suitably to maintain polymerization speed, suppress the distillating of monomer, do not damage the tone, heat endurance, light resistance of final polycarbonate resin etc. simultaneously, the kind of above-mentioned catalyst and amount selected very important.

Preferably use catalyst and utilize 2 above reactors to manufacture with multistage polymerization for polycarbonate resin of the present invention (A). The reason of utilizing 2 above reactors to implement polymerization is: at the polymerisation initial stage, monomer contained in reactant liquor is many, thereby importantly in maintaining needed polymerization speed, suppresses the volatilization of monomer. In addition, in polymerization reaction late stage, in order to make balance to polymerization side shifting, importantly fully the raw monohydroxy compound of by-product is removed in distillation. Like this, from the aspect of production efficiency, in order to set different polymeric reaction conditions, preferably use 2 above polymer reactors of arranged in series.

As mentioned above, the reactor using in method of the present invention is preferably at least more than 2, from aspects such as production efficiencys, more preferably 3 above, more preferably 3～5, be particularly preferably 4.

In the present invention, if reactor is more than 2, in this reactor, can change continuously temperature or pressure, and then there is the stage of reaction that multiple conditions are different.

In the present invention, polymerization catalyst can add in raw material preparation vessel and feed sump, also can directly add in polymerization tank. From the aspect of the stability of supply and the control of polymerization, catalyst supply pipeline is preferably set in the way that is supplied to the feed line before polymerization tank, preferably supply with the aqueous solution.

For polymerisation, specifically, about the reaction temperature of the 1st section, as the maximum temperature of the interior temperature of polymer reactor, be preferably 140 DEG C～270 DEG C, more preferably 180 DEG C～240 DEG C, more preferably 200 DEG C～230 DEG C. Pressure (absolute pressure) is preferably 110kPa～1kPa, more preferably 70kPa～5kPa, 30kPa～10kPa more preferably in addition. Reaction time is preferably 0.1 hour～and 10 hours, more preferably 0.5 hour～3 hours. Preferably produced monohydroxy compound distillation is implemented except going to reaction system to the polymerisation of the 1st section on one side on one side.

About the 2nd section of later polymerisation, preferably make the pressure of reaction system decline at leisure from the pressure of the 1st section, then on one side by the monohydroxy compound of generation except going to reaction system, make the pressure (absolute pressure) of reaction system finally for below 200Pa on one side, thereby implement the 2nd section of later polymerisation. About reaction temperature, the maximum temperature of interior temperature is preferably 210 DEG C～270 DEG C, more preferably 220 DEG C～250 DEG C. Reaction time is preferably 0.1 hour conventionally～and 10 hours, more preferably 1 hour～6 hours, more preferably 0.5 hour～3 hours.

Be more than above-mentioned lower limit by making the temperature of polymerisation, can boost productivity, suppress the thermal process to goods. In addition, by being below the above-mentioned upper limit, can prevent the volatilization of monomer, prevent the decomposition of polycarbonate resin and painted simultaneously.

Particularly in order to suppress the painted and hot deteriorated of polycarbonate resin (A), obtain the good polycarbonate resin of color harmony light resistance (A), the maximum temperature of the interior temperature in the total overall reaction stage is preferably less than 250 DEG C, more preferably 225 DEG C～245 DEG C.

In addition, in order to suppress the reduction of polymerization speed of polymerisation latter half, the degradation inhibiting that thermal process is caused, to Min., is preferably used embolism fluidity and interface to upgrade the horizontal reactor of property excellence in the terminal stage of polymerization.

In order to obtain the polycarbonate resin (A) of predetermined molecular weight, if polymerization temperature is too high, polymerization time is long, there is the tendency that ultraviolet ray transmissivity reduces, YI value increases.

The aspect of effectively applying flexibly from resource, the monohydroxy compound of by-product life is preferably after refining as required, as the raw material recycling of diphenyl carbonate or bisphenol-A etc.

After polycondensation described above, conventionally carry out cooling curing for polycarbonate resin of the present invention (A), and utilize rotary cutter etc. to carry out granulating.

Do not limit for granular method, for example, can enumerate following methods: extract out with molten condition from final polymer reactor, make its cooling curing and carry out granular method with the form of line material; Resin is supplied to molten condition from final polymer reactor the extruder of single screw rod or twin-screw, after melt extruding, makes its cooling curing and carry out granular method; And, extract out with molten condition from final polymer reactor, make its cooling curing and once carrying out granulating with the form of line material, and then resin being supplied to the extruder of single screw rod or twin-screw, after melt extruding, making its cooling curing and carry out granular method; Etc..

Now, in extruder, can be by remaining monomer decompression devolatilization, and can add, mixing known heat stabilizer, nertralizer, ultra-violet absorber, releasing agent, colouring agent, antistatic additive, slip agent, lubricant, plasticizer, bulking agent and fire retardant etc. conventionally.

Melting mixing temperature in extruder depends on glass transition temperature and the molecular weight of polycarbonate resin (A), is conventionally preferably 150 DEG C～300 DEG C, more preferably 200 DEG C～270 DEG C, more preferably 230 DEG C～260 DEG C.

Be more than 150 DEG C by making melting mixing temperature, can suppress the melt viscosity of polycarbonate resin (A), reduce the load to extruder, boost productivity. By being below 300 DEG C, the heat that can suppress Merlon is deteriorated, can cause the reduction of mechanical strength and the generation of painted and gas because of the reduction of molecular weight.

While manufacturing for polycarbonate resin of the present invention (A), in order to prevent sneaking into of foreign matter, wish to arrange filter. The setting position of filter is preferably the downstream of extruder, and in 99% filtering accuracy of removing, the size of removing foreign matter (mesh) of filter is preferably below 100 μ m. Particularly, while not wishing to sneak into small foreign matter in film purposes etc., more preferably 40 μ m following, more preferably below 10 μ m.

About extruding for polycarbonate resin of the present invention (A), for the foreign matter after preventing from extruding is sneaked into, preferably according to the defined grade 7 of JISB9920 (2002), further preferably according to class 6, in the high toilet of cleanliness factor, implement to extrude.

In addition, by extrude polycarbonate resin cooling granulation time, preferably use the cooling means such as the cooling and water-cooled of air. The air using when cooling about air, preferably uses the air of having removed in advance airborne foreign matter with HEPA filter etc., to prevent adhering to again of airborne foreign matter.

Use when water-cooled, preferably use through ion exchange resin etc. and removed the metal ingredient in water and and then removed the water of the foreign matter in water with filter. In 99% filtering accuracy of removing, the mesh of the filter using is preferably 10 μ m～0.45 μ m.

The molecular weight for polycarbonate resin of the present invention (A) obtaining like this can represent with reduced viscosity. More than reduced viscosity is preferably 0.30dL/g conventionally, more preferably more than 0.35dL/g. In addition, the upper limit of reduced viscosity be preferably 1.20dL/g following, more preferably 1.00dL/g following, more preferably below 0.80dL/g.

Be more than above-mentioned lower limit by making the reduced viscosity of polycarbonate resin (A), can fully obtain the mechanical strength of products formed. In addition, by being below the above-mentioned upper limit, the mobility can improve moulding time, boosts productivity and mouldability.

It should be noted that, reduced viscosity is measured as follows: use carrene as solvent, Merlon concentration is critically adjusted to 0.6g/dL, measure with Ubbelohde viscosity tube with 20.0 DEG C ± 0.1 DEG C of temperature.

And then the lower limit amount of the concentration of the end group representing for the following general formula (6) of polycarbonate resin of the present invention (A) is preferably 20 μ eq/g, more preferably 40 μ eq/g, 50 μ eq/g more preferably conventionally. In addition, the upper limit is preferably 160 μ eq/g, more preferably 140 μ eq/g, 100 μ eq/g more preferably conventionally.

If the excessive concentration of end group that following general formula (6) represents, although the tone after just polymerization and when moulding is good, likely causes the deterioration of the tone after ultraviolet ray exposes to the open air, if contrary concentration is too low, heat endurance likely reduces.

The concentration of end group representing in order to control following general formula (6), except controlling as being useful on containing of raw material the dihydroxy compounds of dihydroxy compounds of the present invention and the molar ratio of the carbonic diester that above-mentioned general formula (5) represents, can also enumerate the kind of catalyst and the method for amount, polymerization pressure and polymerization temperature etc. while controlling ester exchange reaction.

In addition, by be used for polycarbonate resin of the present invention (A) and the molal quantity of H aromatic rings bonding be made as (C), by with aromatic rings beyond the molal quantity of H of bonding while being made as (D), represent with C/ (C+D) with respect to the ratio of the molal quantity of whole H with the molal quantity of the H of aromatic rings bonding.

As mentioned above, the aromatic rings with ultraviolet absorption ability likely exerts an influence to light resistance, therefore C/ (C+D) be preferably below 0.1, more preferably below 0.05, more preferably below 0.02, be particularly preferably below 0.01. C/ (C+D) can pass through¹H-NMR is quantitative.

Polycarbonate resin of the present invention can be made article shaped by generally well-known methods such as injection moulding, extrusion moulding and extrinsion pressings.

In addition, before carrying out various moulding, can also utilize as required rotary drum mixer, super blender (SUPERMIXER), floated mixer (フローター for polycarbonate resin of the present invention (A)), the additives such as heat of mixing stabilizing agent, nertralizer, ultra-violet absorber, releasing agent, colouring agent, antistatic additive, slip agent, lubricant, plasticizer, bulking agent and fire retardant such as V-Mixer, nauta mixer (NAUTAMIXER), Banbury and extruder.

More than the glass transition temperature of above-mentioned polycarbonate resin (A) is preferably 75 DEG C and below 105 DEG C, more preferably more than 80 DEG C and below 105 DEG C, more preferably more than 85 DEG C and below 105 DEG C. There is excellent stable on heating products formed by using the polycarbonate resin (A) of glass transition temperature within the scope of this, can providing.

To link with carbonic acid ester bond the polycarbonate resin forming from the construction unit of dihydroxy compounds for aromatic polycarbonate resin of the present invention (B), as long as there is aromatic rings in structure, can use in the past known any polycarbonate resin, also can comprise from the construction unit of dihydroxy compounds with the position that above-mentioned formula (1) represents.

Preferably, the polycarbonate resin using is maximum from the construction unit of dihydroxy compounds with aromatic rings in the entire infrastructure unit from dihydroxy compounds, more preferably, with respect to the entire infrastructure unit from dihydroxy compounds, from the structure of dihydroxy compounds with aromatic rings be 50 % by mole above, more preferably 70 % by mole above, be particularly preferably more than 90 % by mole. Wherein, comprise when thering is the construction unit of dihydroxy compounds at the position that above-mentioned general formula (1) represents, can use the polycarbonate resin different from polycarbonate resin (A) structure.

Can be any of homopolymers and copolymer for aromatic polycarbonate resin of the present invention (B). In addition, aromatic polycarbonate resin (B) can also have branched structure.

More particularly, the polycarbonate resin of repetitive structure representing for thering is following general formula (7).

(in above-mentioned general formula (7), Ar¹、Ar²Represent independently of one another to have or do not have substituent arylene, X represents singly-bound or divalent group)

As having or do not have substituent arylene, as long as arylene is not particularly limited, preferred fragrance ring is 3 following arylene, more preferably phenylene.

As Ar¹、Ar²The substituting group that has independently of one another or do not have, for example can enumerate that to have or do not have substituent carbon number be 1～10 alkyl, have or do not have substituent carbon number is 1～10 alkoxyl, halogen group, the carbon number halogenated alkyl that is 1～10 and to have or do not have substituent carbon number be 6～20 aromatic group.

In these substituting groups, preferably having or do not have substituent carbon number and be 1～10 alkyl and having or do not have substituent carbon number is 6～20 aromatic group, the alkyl that more preferably carbon number is 1～10, particularly preferably methyl.

As divalent group, can enumerate there is or do not have alkylidene that substituent carbon number is 1～6 chain structure, there is or do not have alkylidene that substituent carbon number is 1～6 chain structure, there is or do not have alkylidene that substituent carbon number is 3～6 circulus, there is or do not have alkylidene that substituent carbon number is 3～6 circulus ,-O-,-S-,-CO-and-SO₂-. The substituting group that the alkylidene of the chain structure that is 1～6 as carbon number has, preferred aryl groups, particularly preferably phenyl.

The construction unit from dihydroxy compounds that forms the aromatic polycarbonate resin (B) using in the present invention is to remove hydrogen atom and the construction unit that obtains from the hydroxyl of dihydroxy compounds. As the concrete example of suitable dihydroxy compounds, can enumerate following substances.

4,4 '-xenol, 2,4 '-xenol, 3,3 '-dimethyl-4,4 '-dihydroxy-1,1 '-biphenyl, 3,3 '-dimethyl-2,4 '-dihydroxy-1,1 '-biphenyl, 3,3 '-bis--(tert-butyl group)-4,4 '-dihydroxy-1,1 '-biphenyl, 3,3 ', 5,5 '-tetramethyl-4,4 '-dihydroxy-1,1 '-biphenyl, 3,3 ', 5,5 '-tetra--(tert-butyl group)-4,4 '-dihydroxy-1,1 '-biphenyl and 2,2 ', 3,3 ', 5,5 '-hexamethyl-4,4 '-dihydroxy-1, the biphenol compounds such as 1 '-biphenyl.

Two-(4-hydroxyl-3,5-3,5-dimethylphenyl) methane, two-(4-hydroxyphenyl) methane, two-(4-hydroxy-3-methyl phenyl) methane, 1,1-pair-(4-hydroxyphenyl) ethane, 1,1-pair-(4-hydroxyphenyl) propane, 2,2-pair-(4-hydroxyphenyl) propane, 2,2-pair-(4-hydroxy-3-methyl phenyl) propane, 2,2-pair-(4-hydroxyphenyl) butane, 2,2-pair-(4-hydroxyphenyl) pentane, 2,2-pair-(4-hydroxyphenyl)-3-methybutane, 2,2-pair-(4-hydroxyphenyl) hexane, 2,2-pair-(4-hydroxyphenyl)-4-methylpentane, 1,1-pair-(4-hydroxyphenyl) pentamethylene, 1,1-pair-(4-hydroxyphenyl) cyclohexane, two-(3-phenyl-4-hydroxyphenyl) methane, 1,1-pair-(3-phenyl-4-hydroxyphenyl) ethane, 1,1-pair-(3-phenyl-4-hydroxyphenyl) propane, 2,2-pair-(3-phenyl-4-hydroxyphenyl) propane, 1,1-pair-(4-hydroxy-3-methyl phenyl) ethane, 2,2-pair-(4-hydroxyl-3-ethylphenyl) propane, 2,2-pair-(4-hydroxyl-3-isopropyl phenyl) propane, 2,2-pair-(4-hydroxyl-3-secondary butyl phenenyl) propane, 1,1-pair-(4-hydroxyl-3,5-3,5-dimethylphenyl) ethane, 2,2-pair-(4-hydroxyl-3,5-3,5-dimethylphenyl) propane, 1,1-pair-(4-hydroxyl-3,6-3,5-dimethylphenyl) ethane, two-(4-hydroxyl-2,3,5-trimethylphenyl) methane, 1,1-pair-(4-hydroxyl-2,3,5-trimethylphenyl) ethane, 2,2-pair-(4-hydroxyl-2,3,5-trimethylphenyl) propane, two-(4-hydroxyl-2,3,5-trimethylphenyl) phenylmethane, 1,1-pair-(4-hydroxyl-2,3,5-trimethylphenyl) diphenylphosphino ethane, 1,1-pair-(4-hydroxyl-2,3,5-trimethylphenyl) cyclohexane, two-(4-hydroxyphenyl) phenylmethane, 1,1-pair-(4-hydroxyphenyl)-1-diphenylphosphino ethane, 1,1-pair-(4-hydroxyphenyl)-1-phenyl-propane, two-(4-hydroxyphenyl) diphenyl methane, two-(4-hydroxyphenyl) dibenzyl methane, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (1-methyl ethylidene)] two-[phenol], 4,4 '-[Isosorbide-5-Nitrae-phenylene dimethylene] two-[phenol], 4,4 '-[Isosorbide-5-Nitrae-phenylene two (1-methyl ethylidene)] two-[2,6-xylenol], 4,4 '-[Isosorbide-5-Nitrae-phenylene dimethylene] be two-and [2,6-xylenol], 4,4 '-[Isosorbide-5-Nitrae-phenylene dimethylene] two-[2,3,6-TMP], 4,4 '-[Isosorbide-5-Nitrae-phenylene two (1-methyl ethylidene)] two-[2,3,6-TMP], 4,4 '-[1,3-phenylene two (1-methyl ethylidene)] two-[2,3,6-TMP], 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxy diphenyl sulfide, 3,3 ', 5,5 '-tetramethyl-4,4 '-dihydroxydiphenyl ether, 3,3 ', 5,5 '-tetramethyl-4,4 '-dihydroxy-diphenyl sulfone, 3,3 ', 5,5 '-tetramethyl-4,4 '-dihydroxy diphenyl sulfide, phenolphthalein, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (1-methyl ethenylidene)] bis-phenol, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (1-methyl ethenylidene)] two [2-methylphenols], (2-hydroxyphenyl) (4-hydroxyphenyl) methane, (2-hydroxy-5-methyl base phenyl) (4-hydroxy-3-methyl phenyl) methane, 1,1-(2-hydroxyphenyl) (4-hydroxyphenyl) ethane, the bisphenol compounds such as 2,2-(2-hydroxyphenyl) (4-hydroxyphenyl) propane and 1,1-(2-hydroxyphenyl) (4-hydroxyphenyl) propane.

The halogenation bisphenol compounds such as two (the bromo-4-hydroxyphenyl of 3, the 5-bis-) propane of 2,2-and two (the chloro-4-hydroxyphenyl of 3, the 5-bis-) propane of 2,2-.

Among these, preferred dihydroxy compounds can be enumerated two-(4-hydroxyl-3, 5-3,5-dimethylphenyl) methane, two-(4-hydroxyphenyl) methane, two-(4-hydroxy-3-methyl phenyl) methane, 1, 1-pair-(4-hydroxyphenyl) ethane, 2, 2-pair-(4-hydroxyphenyl) propane, 2, 2-pair-(4-hydroxy-3-methyl phenyl) propane, 2, 2-pair-(4-hydroxyl-3, 5-3,5-dimethylphenyl) propane, 1, 1-pair-(4-hydroxyphenyl) cyclohexane, two-(4-hydroxyphenyl) phenylmethane, 1, 1-pair-(4-hydroxyphenyl)-1-diphenylphosphino ethane, 1, 1-pair-(4-hydroxyphenyl)-1-phenyl-propane, two-(4-hydroxyphenyl) diphenyl methane, 2-hydroxyphenyl (4-hydroxyphenyl) methane and 2, 2-(2-hydroxyphenyl) (4-hydroxyphenyl) propane etc. links by alkylidene the bisphenol compound that phenol forms.

Among these, particularly preferably two-(4-hydroxyphenyl) methane, two-(4-hydroxy-3-methyl phenyl) methane, two-(4-hydroxyl-3,5-3,5-dimethylphenyl) methane, 2,2-pair-(4-hydroxyphenyl) propane, 2,2-pair-(4-hydroxy-3-methyl phenyl) propane, 2,2-pair-(4-hydroxyl-3,5-3,5-dimethylphenyl) propane and 1,1-be two-and the carbon number of the alkylidene such as (4-hydroxyphenyl) cyclohexane is the bisphenol compound below 6.

Manufacture method for aromatic polycarbonate resin of the present invention (B) can be used the known any means in the past such as phosgenation, ester-interchange method and pyridine method. Below, as an example, the manufacture method of the aromatic polycarbonate resin (B) that utilizes ester-interchange method is described.

Ester-interchange method is following manufacture method: in dihydroxy compounds and carbonic diester, add base catalyst, and then add the acidic materials of this base catalyst of neutralization, carry out melt transesterification polycondensation. As dihydroxy compounds, for example, can enumerate above-mentioned illustrative biphenol compound and bisphenol compound.

As the typical example of carbonic diester, can enumerate the diaryl carbonates such as diphenyl carbonate, carboxylol ester, two (chlorphenyl) carbonic ester, two tolyl carbonic esters, dinaphthyl carbonic ester and two (biphenyl) carbonic esters; The dialkyl carbonates such as diethyl carbonate, dimethyl carbonate, dibutyl carbonate and carbonic acid two cyclohexyls. Among these, particularly preferably use diphenyl carbonate.

From the aspect of the balance of mechanical characteristic and processing and forming, for the viscosity average molecular weigh of aromatic polycarbonate resin of the present invention (B) be generally more than 8,000, be preferably below 30,000, more preferably 10, more than 000 and below 25,000.

In addition, the reduced viscosity of above-mentioned aromatic polycarbonate resin (B) is measured as follows: use carrene as solvent, Merlon concentration is critically adjusted to 0.60g/dl, measure with 20.0 DEG C ± 0.1 DEG C of temperature, more than reduced viscosity is preferably 0.23dl/g conventionally and below 0.72dl/g, more preferably more than 0.27dl/g and below 0.61dl/g.

It should be noted that, in the present invention, aromatic polycarbonate resin (B) can only use separately one, or also can be use mixing two or more.

Poly carbonate resin composition (X) in the present invention comprises polycarbonate resin (A) and aromatic polycarbonate resin (B), and the part that this polycarbonate resin (A) comprises to come self-structure has the construction unit (a) of the dihydroxy compounds at the position that following general formula (1) represents.

Aromatic polycarbonate resin (B) more than shared ratio is generally 30 % by weight in the above-mentioned poly carbonate resin composition (X) that comprises polycarbonate resin (A) and aromatic polycarbonate resin (B), be preferably 35 % by weight more than, more preferably more than 45 % by weight, more preferably more than 55 % by weight. On the other hand, be preferably 90 % by weight following, more preferably 80 % by weight following, more preferably below 70 % by weight.

Be below the above-mentioned upper limit by making aromatic polycarbonate resin (B) shared ratio in poly carbonate resin composition (X), can suppress yellow colour index (YI) value after sunlight weather resistance test case exposure experiment described later. In addition, if aromatic polycarbonate resin (B) shared ratio in poly carbonate resin composition (X) is less than 30 % by weight, the YI value at initial stage has the tendency of increase.

From keeping the transparent aspect of poly carbonate resin composition and polycarbonate resin moldings, poly carbonate resin composition (X) the preferred glass transition temperature in the present invention is single.

In addition, as long as the polycarbonate resin (A) in poly carbonate resin composition (X) is variety classes with aromatic polycarbonate resin (B). As polycarbonate resin (A), preferably there is ring structure, wherein particularly preferably comprise isobide.

Resin beyond<polycarbonate resin>

Poly carbonate resin composition of the present invention and polycarbonate resin moldings can also mixture polycarbonate resin resin and resin additives in addition in addition.

As in order further to improve and to adjust moulding processability and each physical property and the concrete example of resin beyond the polycarbonate resin of mixture, can enumerate the random of the resins such as polyester based resin, polyethers, polyamide, polyolefin and polymethyl methacrylate and core-shell type, graft type or wire and rubber-like modifier that block copolymer is such etc.

With respect to mixture 100 weight portions for polycarbonate resin of the present invention (A) and aromatic polycarbonate resin (B), as the mixture amount of the resin beyond above-mentioned polycarbonate resin, preferably with the ratio mixture more than 1 weight portion and below 30 weight portions, more preferably with the ratio mixture more than 3 weight portions and below 20 weight portions, further preferably with the ratio mixture more than 5 weight portions and below 10 weight portions.

The reduction of molecular weight and the deterioration of tone when preventing moulding, can mixture heat stabilizer in poly carbonate resin composition of the present invention and polycarbonate resin moldings.

As above-mentioned heat stabilizer, can enumerate phosphorous acid, phosphoric acid, phosphonous acid and phosphonic acids and their ester etc. specifically, for example can enumerate triphenyl phosphite, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, tridecyl phosphite, tricresyl phosphite monooctyl ester, tricresyl phosphite (octadecyl) ester, phosphorous acid didecyl list phenylester, phosphorous acid dioctyl list phenylester, phosphorous acid diisopropyl list phenylester, phosphorous acid monobutyl diphenyl, phosphorous acid list decyl diphenyl, phosphorous acid list octyl group diphenyl, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, 2,2-di-2-ethylhexylphosphine oxide (4,6-di-tert-butyl-phenyl) octyl group phosphite ester, two (nonyl phenyl) pentaerythritol diphosphites, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, the adjacent Biphenyl Ester of di(2-ethylhexyl)phosphate phenyl list, dibutylphosphoric acid ester, dioctylphosphoric acid ester, diisopropyl phosphate, 4,4 '-biphenylene diphosphinic acid four (2,4-di-tert-butyl-phenyl) ester, phenyl-phosphonic acid dimethyl ester, phenyl-phosphonic acid diethylester and phenyl-phosphonic acid dipropyl etc.

Wherein, preferably use Wytox 312, trimethyl phosphate, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites and phenyl-phosphonic acid dimethyl ester.

These heat stabilizers can use separately one, also can share two or more. With respect to mixture 100 weight portions for polycarbonate resin of the present invention (A) and aromatic polycarbonate resin (B), the mixture amount of above-mentioned heat stabilizer is preferably with the ratio mixture more than 0.0001 weight portion and below 1 weight portion, more preferably with the ratio mixture more than 0.0005 weight portion and below 0.5 weight portion, further preferably with the ratio mixture more than 0.001 weight portion and below 0.2 weight portion.

By with above-mentioned scope mixture heat stabilizer, can there is not oozing out of additive etc., can prevent that the molecular weight of resin from reducing and variable color.

In addition, for anti-oxidant, can the generally well-known antioxidant of mixture in poly carbonate resin composition of the present invention and polycarbonate resin moldings.

As above-mentioned antioxidant, can enumerate for example pentaerythrite four (3-mercaptopropionic acid ester), pentaerythrite four (3-lauryl thiopropionate), glycerine-3-stearyl thiopropionate, triethylene glycol-bis-[3-(the 3-tert-butyl group-5-methyl-4-hydroxyphenyl) propionic ester], 1, 6-hexylene glycol-bis-[3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionic ester], pentaerythrite-tetra-[3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionic ester], octadecyl-3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionic ester, 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, N, N-hexa-methylene two (3, 5-di-t-butyl-4-hydroxyl-hydrocinnamamide), 3, 5-di-t-butyl-4-hydroxyl-benzylphosphonic acid ester-diethyl ester, three (3, 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 4, 4 '-biphenylene diphosphinic acid four (2, 4-di-tert-butyl-phenyl) ester and 3, 9-two { 1, 1-dimethyl-2-[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propiono oxygen base] ethyl }-2, 4, 8, 10-tetra-oxaspiros (5, 5) one kind or two or more in hendecane etc.

With respect to mixture 100 weight portions for polycarbonate resin of the present invention (A) and aromatic polycarbonate resin (B), the mixture amount of above-mentioned antioxidant is preferably with the ratio mixture more than 0.0001 weight portion and below 1 weight portion, more preferably with the ratio mixture more than 0.0005 weight portion and below 0.5 weight portion, further preferably with the ratio mixture more than 0.001 weight portion and below 0.2 weight portion.

By with above-mentioned scope mixture antioxidant, can there is not antioxidant the oozing out and the reduction of the mechanical property of various products formeds of formed body surface, can prevent the oxidative degradation of resin.

<ultra-violet absorber>

In order further to improve the weatherability of poly carbonate resin composition of the present invention and polycarbonate resin moldings, can mixture ultra-violet absorber.

As above-mentioned ultra-violet absorber, can enumerate for example 2-(2 '-hydroxyl-5 '-tertiary octyl phenyl) BTA, 2-(the 3-tert-butyl group-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(5-methyl-2-hydroxyphenyl) BTA, 2-[2-hydroxyl-3, two (the α of 5-, α-dimethylbenzyl) phenyl]-2H-BTA, 2,2 '-di-2-ethylhexylphosphine oxide (4-cumyl-6-BTA phenyl) and 2,2 '-TOPOT 2,2′ p phenylenebis (1,3-benzoxazine-4-ketone) etc.

As the fusing point of ultra-violet absorber, be particularly preferably the scope of 120～250 DEG C. Be 120 DEG C of above ultra-violet absorbers if use fusing point, the fuzzy minimizing causing because of gas on products formed surface, this problem is improved.

Specifically, for example use 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) BTA, 2-(the 2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-[2 '-hydroxyl-3 '-(3 "; 4 " 5 "; 6 "-tetrahydric phthalimide methyl)-5 '-aminomethyl phenyl] BTA, 2,2-di-2-ethylhexylphosphine oxide [4-(1,1,3,3-tetramethyl butyl) BTA such as-6-(2H-BTA-2-yl) phenol and 2-(2-hydroxyl-3,5-dicumylphenyl) BTA is ultra-violet absorber. Among these, particularly preferably 2-(2-hydroxyl-3,5-dicumylphenyl) BTA, 2,2-di-2-ethylhexylphosphine oxide [4-(1,1,3,3-tetramethyl butyl)-6-(2H-BTA-2-yl) phenol.

Above-mentioned ultra-violet absorber can use separately one, also can share two or more. With respect to mixture 100 weight portions for polycarbonate resin of the present invention (A) and aromatic polycarbonate resin (B), the mixture amount of above-mentioned ultra-violet absorber is preferably with the ratio mixture more than 0.0001 weight portion and below 1 weight portion, more preferably with the ratio mixture more than 0.0005 weight portion and below 0.5 weight portion, further preferably with the ratio mixture more than 0.001 weight portion and below 0.2 weight portion.

In the time of above-mentioned scope, can there is not ultra-violet absorber the oozing out and the reduction of the mechanical property of various products formeds of ultra-violet absorber products formed surface in mixture amount, can improve the weatherability of resin combination and products formed.

In addition, in order further to improve the weatherability of poly carbonate resin composition of the present invention and polycarbonate resin moldings, can mixture hindered amine be light stabilizer.

Be light stabilizer as above-mentioned hindered amine, for example can enumerate two (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, two-(1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, poly-[[6-(1, 1, 3, 3-tetramethyl butyl) amino-1, 3, 5-triazine-2, 4-bis-bases] [(2, 2, 6, 6-tetramethyl-4-piperidyl) imino group] hexa-methylene [(2, 2, 6, 6-tetramethyl-4-piperidyl) imino group]], N, N '-bis-(3-aminopropyl) ethylenediamine-2, two [N-butyl-the N-(1 of 4-, 2, 2, 6, 6-pentamethyl-4-piperidyl amino)-6-chloro-1, 3, 5-triazine condensation product and dibutyl amine 1, 3, 5-triazine N, N '-bis-(2, 2, 6, 6)-tetramethyl-4-piperidyl-1, 6-1, 6-hexamethylene diamine and N-(2, 2, 6, 6-tetramethyl-4-piperidyl) condensation polymer etc. of butylamine. wherein, preferably two (2,2,6,6-tetramethyl-4-piperidyl) sebacates and two-(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

With respect to mixture 100 weight portions for polycarbonate resin of the present invention (A) and aromatic polycarbonate resin (B), above-mentioned hindered amine is the preferably ratio mixture above and below 1 weight portion with 0.001 weight portion of mixture amount of light stabilizer, further preferably with the ratio mixture more than 0.005 weight portion and below 0.5 weight portion, particularly preferably with the ratio mixture more than 0.01 weight portion and below 0.2 weight portion.

By being light stabilizer with above-mentioned scope mixture hindered amine, can there is not hindered amine and be light stabilizer the oozing out and the reduction of the mechanical property of various products formeds of poly carbonate resin composition surface, can improve the weatherability of the products formed that poly carbonate resin composition moulding of the present invention is formed.

The antistick characteristic departing from from metal die during for further raising melt molding, poly carbonate resin composition of the present invention preferably also contains releasing agent. As releasing agent, the natural animal such as high-grade aliphatic ester, beeswax that for example can enumerate higher fatty acids, monobasic or polyalcohol is that the natural oils such as the natural plant such as wax, Brazil wax wax, solid paraffin are that the natural coal such as wax, montan wax is wax, olefin-based wax, silicone oil and organopolysiloxane etc. Wherein, the high-grade aliphatic ester of higher fatty acids and monobasic or polyalcohol particularly preferably.

As high-grade aliphatic ester, preferably replace or be that 1～carbon number is 20 monohydric alcohol or polyalcohol with replacement or is that 10～carbon number is the partial ester that forms of 30 saturated fatty acid or ester entirely without the carbon number replacing without the carbon number replacing.

As partial ester or the full ester of above-mentioned monohydric alcohol or polyalcohol and saturated fatty acid, for example can enumerate glyceryl monostearate, stearic acid two glyceride, stearic acid triglyceride, stearic acid list sorbitol ester, stearic acid stearyl ester, behenic acid monoglyceride, behenic acid docosyl ester, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythrite four pelargonates, propylene glycol monostearate, stearyl stearate, palmitic acid palm ester, butyl stearate, methyl laurate, isopropyl palmitate, diphenic acid Biphenyl Ester (PVC Off エニ Le PVC Off エネ mono-ト), sorbitan monostearate and stearic acid-2-Octyl Nitrite etc.

Wherein, preferably use glyceryl monostearate, stearic acid triglyceride, pentaerythritol tetrastearate and behenic acid docosyl ester.

As higher fatty acids, preferably replacement or the carbon number without replacement are that 10～carbon number is 30 saturated fatty acid. As such saturated fatty acid, can enumerate myristic acid, laurate, palmitic acid, stearic acid, behenic acid etc. These releasing agents can use separately one, also can be use mixing two or more.

With respect to mixture 100 weight portions for polycarbonate resin of the present invention (A) and aromatic polycarbonate resin (B), the content of this releasing agent be preferably 0.0001 weight portion above, more preferably 0.01 weight portion above, more preferably more than 0.1 weight portion. In addition, be preferably 2 weight portions following, more preferably 1 weight portion following, more preferably below 0.5 weight portion.

In present embodiment, the interpolation period, the adding method that are compounded into the above-mentioned releasing agent in poly carbonate resin composition are not particularly limited.

As interpolation period, can enumerate: for example, while termination for polymerisation in the situation that utilizing ester-interchange method to manufacture polycarbonate resin; And then, no matter be which kind of polymerization, can enumerate the state of the medium polycarbonate resin melting in mixing way of polycarbonate resin and other mixed agents; Use extruder etc. to mix with the polycarbonate resin of the solid state such as particle or powder when mixing; Etc..

As adding method, for example, there is following method: above-mentioned releasing agent is directly mixed or mixing method in polycarbonate resin; Use a small amount of polycarbonate resin or other resins etc. and above-mentioned releasing agent to make the masterbatch of high concentration, add with the form of the masterbatch of this high concentration.

In present embodiment, obtain the polycarbonate resin moldings that above-mentioned poly carbonate resin composition moulding is formed. Forming method for polycarbonate resin moldings is not particularly limited, for example can enumerate following methods: polycarbonate resin (A), aromatic polycarbonate resin (B) and the raw material such as other resins and additive as required are directly mixed, drop into extruder or injection (mo(u)lding) machine and carry out moulding; Or, use double screw extruder by above-mentioned raw materials melting mixing, extrude and make after particle with line material shape, this particle input extruder or injection (mo(u)lding) machine are carried out to moulding.

In addition, the light resistance of polycarbonate resin moldings of the present invention, transparency excellence, therefore can be used in road sound-proof wall, arcade suspended ceiling piece, arcade ceiling, facility roof and facility wall material etc.

The treatment with irradiation of the use sun shine carbon arc lamp in the present invention as described later, it refers to and utilizes specific device, use specific filter etc., be at blackboard temperature that 63 DEG C, relative humidity are 50%, the rainfall spray time of every 1 hour is under the environment of 12 minutes, uses sun shine carbon arc lamp, with discharge voltage 50V, discharge current 60A, sample illumination wavelength is mainly to the above and light below 1100nm of 300nm 500 hours.

Using above-mentioned sun shine carbon arc lamp to carry out 500 hours total light transmittances after treatment with irradiation to the formed body (thickness 3mm) being obtained by poly carbonate resin composition moulding of the present invention is preferably more than 85%, the upper limit is preferably below 99%, and the difference of yellow colour index (YI) value before and after this treatment with irradiation is preferably below 10, more preferably below 8, more preferably below 6.

Embodiment

Below, illustrate in greater detail the present invention by embodiment, but only otherwise exceed its main points, the present invention is not subject to the restriction of following examples.

Below, carry out the physical property of polycarbonate resin, poly carbonate resin composition, products formed etc. or the evaluation of characteristic by following method.

(1) mensuration of reduced viscosity

Use carrene as solvent, the sample of dissolved polycarbonate resin combination, the polycarbonate solution that preparation concentration is 0.6g/dL. The Ubbelohde viscosity tube that uses the industrial society of gloomy friendly physics and chemistry to manufacture, measures with 20.0 DEG C ± 0.1 DEG C of temperature, by the time of the passing through t of solvent₀Obtain relative viscosity η rel with the time of the passing through t of solution according to following formula,

ηrel=t/t₀

Obtain specific viscosity η sp by relative viscosity according to following formula.

ηsp=(η－η₀)/η₀=ηrel－1

Specific viscosity, divided by concentration c (g/dL), is obtained to reduced viscosity η sp/c. This value is higher, and molecular weight is larger.

(2) tone is measured

According to JISK7105 (1981), use light splitting colour difference meter (the Japanese electric look industry manufacture SE2000 of society), measure yellow colour index (YI) value that is injected into matrix (width 60mm × length 60mm × thickness 3mm) with illuminant-C penetrant method. YI value is less, indicates without yellow sense, excellent quality.

(3) total light transmittance is measured

According to JISK7105 (1981), use haze meter (the Japanese electric look industry manufacture NDH2O00 of society), measure the total light transmittance that is injected into matrix with D65 light source.

(4) sunlight weather resistance test case exposure experiment

According to JISB7753 (2007), use SUGATESTINSTRUMENTS society to manufacture sunlight weather resistance test case S80, utilize sun shine carbon arc lamp (extra long life carbon-carbon 4 to) light source, be set as discharge voltage 50V, discharge current 60A, by irradiating and surface spray (rainfall) is, under 63 DEG C, the relative humidity condition that is 50%, the foursquare face of the flat board (width 60mm × length 60mm × thickness 3mm) that is injected into matrix is carried out to 500 hours treatment with irradiation at blackboard temperature. Surface spray (rainfall) time is made as 12 minutes/and 1 hour. Glass filter uses A type. Measure YI and total light transmittance after treatment with irradiation, and then obtain the poor of 500 hours YI after treatment and YI before treatment.

PC1: from the construction unit of isobide/from construction unit=40/60 of 1,4-CHDM % by mole, reduced viscosity 0.63dl/g

PC2: from the construction unit of isobide/from construction unit=70/30 of 1,4-CHDM % by mole, reduced viscosity 0.51dl/g

PC3: engineering plastics society of Mitsubishi manufactures NOVAREX7022J (only having the aromatic polycarbonate resin from the structure of 2,2-pair-(4-hydroxyphenyl) propane, viscosity average molecular weigh 22,000)

(embodiment 1)

After PC1 and PC3 are dry mixed with the ratio of weight ratio 60:40, the double screw extruder (TEX30HSS-32) that uses society of JSW to manufacture is extruded with 250 DEG C of resin temperatures, after water cooling curing, utilizes rotary cutter to carry out granulating. By particle under blanket of nitrogen in 80 DEG C after dry 10 hours, be supplied to injection (mo(u)lding) machine (society of JSW manufactures J75EII type), be that 250 DEG C, metal die temperature are that 60 DEG C, molding cycle are under the condition of 40 seconds at resin temperature, be injected into the moulding of template (width 60mm × length 60mm × thickness 3mm).

For obtained sample, carry out the mensuration of total light transmittance, YI, the results are shown in table 1.

(embodiment 2)

Except PC1 and PC3 are mixed than the ratio of 40:60 with mixed weight, utilize the method identical with embodiment 1 to carry out making, the evaluation of sample. The results are shown in table 1.

(comparative example 1)

Only PC3 is dried to 6 hours with 120 DEG C under blanket of nitrogen, then be supplied to injection (mo(u)lding) machine (society of JSW manufactures J75EII type), be that 280 DEG C, metal die temperature are that 80 DEG C, molding cycle are the moulding that is injected into template (width 60mm × length 60mm × thickness 3mm) under the condition of 40 seconds at resin temperature, carry out in addition the evaluation identical with embodiment 1. The results are shown in table 1.

(comparative example 2)

Except PC2 and PC3 are mixed than the ratio of 80:20 with mixed weight, utilize the method identical with embodiment 1 to carry out making, the evaluation of sample. The results are shown in table 1.

Table 1

In table 1, "-" represents not use this material.

From these results, it is more than 85% high permeability that poly carbonate resin composition of the present invention all has total light transmittance, and the transparency is excellent, has all maintained the low YI value below 10, tone excellence before and after sunlight weather resistance test case exposure experiment simultaneously. And the difference of the YI value before and after this exposure experiment is also below 10, weatherability is also excellent.

Below at length and with reference to specific embodiment describe the present invention, but it will be apparent to one skilled in the art that and can under the prerequisite that does not depart from spirit and scope, carry out various changes or correction to the present invention. The Japanese patent application (Japanese Patent Application 2010-185056) that the Japanese patent application (Japanese Patent Application 2009-288107) of submitting in the Japanese patent application (Japanese Patent Application 2009-280865) that the application submitted to based on December 10th, 2009, on December 18th, 2009, on August 20th, 2010 submit to, introduces this description with the form of reference by its content.

Claims

1. a poly carbonate resin composition, it is for comprising polycarbonate resin (A) and aromatic copolycarbonateThe poly carbonate resin composition (X) of resin (B), this polycarbonate resin (A) comprises construction unit (a), described inThe dihydroxy compounds that construction unit (a) represents from following formula (2), described aromatic polycarbonate resin (B) stickyAverage molecular weight is more than 8000, below 30000, it is characterized in that above-mentioned aromatic polycarbonate resin (B)In above-mentioned poly carbonate resin composition (X) shared ratio be more than 30 % by weight to 70 % by weight,

Above-mentioned polycarbonate resin (A) comprises from other dihydroxy compounds beyond above-mentioned dihydroxy compoundsConstruction unit, these other dihydroxy compounds are 1,4-CHDM,

Be that 63 DEG C, relative humidity are 50%, the rainfall spray time of every 1 hour is 12 minutes at blackboard temperatureEnvironment under, use sun shine carbon arc lamp with discharge voltage 50V, discharge current 60A to by above-mentioned poly-carbonic acidEster resin composition moulding and formed body that the thickness that obtains is 3mm carries out after 500 hours treatment with irradiation, totalLight transmittance is more than 85%, and the difference of the yellow colour index YI value of these treatment with irradiation front and back is below 10.

2. a polycarbonate resin moldings, is characterized in that, this polycarbonate resin moldings is to pass throughPoly carbonate resin composition moulding claimed in claim 1 is obtained.